Imidazoline derivatives and process



2,781,357 IMIDAZOLINE DERIVATIVES AND PROCESS Hans S. Mannheimer, New York, N. Y., assignor to John J. McCabe, In, New Brunswick, N. J., and said Hans S. Mannheimer, as joint venturers No Drawing. Application December 3,1954,

Serial No. 473,043

14 Claims. (Cl. 260309.6)

This invention relates to novel compositions and to methods for producing them. In one of its more specific aspects the invention is directed to methods of making and to novel derivatives of metal salts of substituted quaternary hydroxy cycloimidinic acid metal alcoholates, examples of which are disclosed in my U. S. Patent 2,528,- 378 and which I shall hereafter refer to herein as cyclo imidates.

Said cycloimidates have been found useful because they have high detergent, foaming, wetting, emulgating, emulsifying, dispersing, bacteriastatic, bacteriacidal, fungicidal, and deodorizing characteristics. They are highly water-soluble, stable in aqueous solutions in the pH range of 1-14 and are not precipitated out of solution by the salts normally present in hard water. They are nonvesicant and non-toxic to human and animal life and may be introduced into theblood stream without ill effects.-

They are surface active agents and serve as excellent synthetic detergents, softeners and dye assistants in the textile and related fields and especially in washing and cleansing of cotton fibers and textiles. They may also be employed as therapeutic agents and are especially useful as germicides, fungicides and antisepticides.

Said cycloimidates have the following general Formula I:

or any one of the aforesaid groups either unsubstituted or hydroxy substituted and having a single either (-O) Patented Feb. 12, 1957 mere physical combination of said agents and that no reaction would occur between them.

Said cycloimidates normally behave anionically in aqueous solutions having a pH above 7, and consequently it was expected that said cycloimidates when in aqueous solution together with anionic surface agents that they would be combined physically only and that no' other reaction would occur therebetween. In the course of my experimentations, I have discovered that said cycloimidates" could be reacted with certain anionic surface active agents at a pH above 7 to produce water-soluble reaction products. Not only did I make said discovery, but I, furor keto (CO) linkage therein, illustrative examples of i or formation of water insoluble compounds; and that adding an anionic surface active agentto an aqueous solution of another anionic surface active agent resulted in a ther discovered that water solutions of such reaction products had viscosities greater than corresponding aqueous solutions of the cycloimidates and also exhibited better foaming characteristics than did said cycloimidates in very low dilutions under extreme water hardness conditions. Said reaction products are non-toxic and nonirritating to the human skin. They have been found eminently useful as general utility detergents, such as for car washing, dish washing, clothes washing, etc. Said cycloimidates when used as components of shampoos sometimes caused slight irritation or stinging of the eyes when such shampoos were used and Water solutions there of accidentally reached the eyes. I have further discovered that the reaction products of this invention caused practically no irritation or stinging of the eyes when so employed.

According to this invention, one or a combination of two or more of said cycloimidates of the general structural Formula I are reacted with one or a combination of two or more anionic surface active agents of the following general structural Formula II to provide novel, water-soluble compounds having the following general structural Formula III, and having high wetting, detergency and surface active properties and capable of providing voluminous and stable foams in aqueous solutions, and which aqueous solutions are substantially non-irritating to the skin and eyes of normal human beings.

N CHa V A I Rr-OH wherein R3 is a hydrocarbon radical, either aliphatic containing 6-18 carbon atoms, or aliphatic-aromatic consisting of a benzene ring or a naphthalene ring having an aliphatic group of 6-18 carbon atoms attached thereto; X is 0803 or S03; and M, R and R2 have been heretofore defined in Formula I.

According to this invention, I react a compound of Formula l with a compound of Formula II to provide the novel and highly useful compounds of Formula III. In general this reaction is carried out in a solution containing compounds I and II and to which a quantity of an acidic agent such as a strong mineral acid, as for example hydrochloric, sulphuric or its equivalent, has been added to lower the pH of the solution to a value of approximately 7 to approximately 9 and while maintaining the mass at a temperature between approximately IUD-200 F. In this reaction under the aforesaid conditions, the quaternary hydroxy of the compound of Formula I combines with the metal of the compound of Formula II to produce the metal hydroxy and the metal of the OM group of the compound of Formula I is replaced by hydrogen due to the acidic agent addition which also at least in part reacts with the formed metal hydroxy compound to, form a Water-soluble salt. The resultant solution can be used directly as a surface active agent, wetting agent or detergent for the, purposes indicated for the cycloimidates. While the quantities of the compound of Formula I and compound of Formula II may be equimolecular for good yield of compounds of Formula III,.I may employ an excess of either, and in general the mole ratio of a compound of Formula I to compound of Formula II may be 2 moles. of the former to 13 moles of the latter.

One of the specific methods which I prefer tov employ in carrying out an, aspect of this inventionris, to first dissolve, a compound of Formula I. in water and. then the pH thereof is. adjusted to approximately 12-13 (measured. electrically) by the addition of aqueous caustic soda if required, so. that when a compound of Formula IIv is added thereto, the pH of thesolution of I and II will be at least and generally 105-11. The temperature of said. solution is raised to 100-200 F. and preferably in factory practice to approximately 140 P. Then a quantity of a compound of Formula II is, dissolved in, water in a separate container and this solution is added to said first. solution and the mass is, maintained, in Saidtemperature range while being constantly stirred, and an acidic agent is added thereto to reduce the pH thereof to a value below 10 and in the range of, approximately 7 to 9, and preferably of. approximately 8.2 to. approximately 8.7. At the end of the acidic agent addition the stirring is continued and the, temperature of the mass maintained for about 10-20 minutes after which the solution is allowed to cool and is a finished product.

The following are specific examples merely given by way of illustrating the invention and are not to. be taken by Way of limitation, all parts being given by weight unless otherwise specified.

Example 1 An aqueous solution of 400 parts of the lauric cycloimidates, of Example 1 of my heretofore identified patent, in 600 parts of water is heated to approximately 140 F. and its pH (measured electrically) is adjusted by the addition of aqueous, caustic soda to 12-13. While being constantly stirred and maintained at that temperature there is added a. solution of 290 parts of sodium salt of lauryl sulfate:

in 600 parts of water. Then while stirring and the tern perature is maintained there is slowly added thereto hydrochloric acid solution (32%) until the pH of the mass is lowered to a value in the range of 8.2 to 8.7. Stirring is continued and the temperature maintained for about 10 minutes more. The resultant product. is a, solution of the novel reaction product having the. following formula:

Cam-OH L I/ Employ the same procedure and components as set forth in Example 1 except that only about 150 parts of the sodium salt of lauryl sulfate are used. In this instance the resultant product is a solution of the reaction product whose structural formula is shown in Example 1 together with unreacted lauric cycloimidate used.

Employ the same procedure as that set forth in Example l, but employ the components indicated in the following Examples 3-5 the quantity of hydrochloric acid solution 2%). is, variablev to, lower the. pH to.v values indicated in Example 1 to obtain the reaction products of said Examples 3-5.

Example 3 400 parts of lauroyl cycloirnidatej (same. as Example 1) in 600 parts of water. 360 parts of stearyl' sulfonate sodium salt:

0 C1sH3'z. SO3Na L in 700 parts of water.

FORMULA OE" REACTION PRODUCT Example, 4

in 500 parts of Water.

FORMULA OF REACTION PRODUCT CH: N om l CaHt-OH nHxr- J- om-ooom CnHza Example 5 400 parts of lauroyl cycloimidate (same as Example 1) in 600 parts of water.

380 parts of hexylnaphthene sulfonate sodium salt:

SOs-INS, l

CoHiu inGQQ parts of: water.

imidates of my herein-before, identified patent, such as those'of Examples 2; 4; 5, 6; 7,8; 101'4;therein; and in addition the specificreactants I- may difier from those employed herein in the radicalflk which may' be a hydro.-

carbon radical of less or more carbon atoms; but in all a nas? cases being at least 4 carbon atoms and preferably 4-18 carbon atoms, and also other hydrocarbon radicals Rs than those specifically used herein may also be employed to provide a great variety of specific compounds illustrating the present invention.

It is to be understood that instead of first adjusting the pH of the cycloimidate to 12-13 before the addition of the compound of Formula II, any other method may be employed to obtain the condition whereby the pH of the solution of I and II is at least 10 and preferably 10.5-11 before the addition of the acidic agent to lower the pH of the mass to approximately 7 to approximately 9. For example, I and II may be dissolved together and this solution may by the addition of caustic soda when required have its pH adjusted to at least 10, and then at 100-20Q F. is ready for the addition of the acidic agent to lower its pH to approximately 7 to approximately 9. If desired, the required amount of acidic agent may be added either before or after the solution at pH of at least 10 is brought to a temperature in the range of 100-200 F.

Since certain changes in carrying out the aforesaid processes and certain modifications in the compositions which embody the invention maybe made without departing from its scope, it is intended that all matter contained in the description shall be interpreted as illustrative and not in a limiting sense.

It is also to be understood that the following claims are intended .to cover all the generic and specific features of the invention herein described, and all statements of the scope of the invention which as a matter of language might be said to fall therebetween.

I claim: 1. A novel compound of the following formula:

/Cgz N, CH:

in which R is a hydrocarbon radical of 4 to 18 carbon atoms; R2. is an organic group selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms, (b) hydroxy substituted aliphatic hydrocarbon groups of 1-4 carbon atoms, (0) aliphatic ether groups, each of said ether groups having a single ether linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ether groups each of said groups having a single ether linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (f) aliphatic keto groups, each of said groups having a single keto linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon'atoms; R3 is a hydrocarbon radical selected from the group consisting of (h) aliphatic hydrocarbon radicals of 6-18 carbon atoms and (i) aliphatic-aromatic hydrocarbon radicals consisting of benzene and naphthalene groups each having an aliphatic hydrocarbon radical of 6-18 carbon atoms attached thereto; X is selected from the group consisting of S03 and 0503; and M is an alkali metal.

2. A novel compound of the following formula:

N CHa rim-000m Rz-OSO:

in which R is a hydrocarbon radical of 4 to 18 carbon carbon atoms X and S03.

3. A novel'compound of the following formula:

atoms, and R3 is an aliphatic hydrocarbon radical of 6-18 in which R is a hydrocarbon radical of 4 to 18 carbon 15 atoms, R4 is an aliphatic hydrocarbon radical of 6-18 carbon atoms.

4. A novel compound of the following formula:

- in which R is a hydrocarbon radical of 4 to 18 carbon atoms and R4 is an .aliphtic hydrocarbon radical of 6-18 carbon atoms.

5. A novel compound of the following formula:

Ciz aa 8. The method comprising under pH conditions of ap proximately 7 to approximately 9 reacting with each other 65 compounds of the following Formulas I and II:

FORMULA I OH; 70 N/ \CH:

Rs-OM Rll-N l Ra-COOM 76 on 7 FORMULA II Rx-X-M in which R is a hydrocarbon radical of 4 to 18 carbon atoms; Rz is an organic group selected from the class consisting of (a) aliphatic hydrocarbon groups of 1-4 carbon atoms, (b) hydroxy substituted aliphatic hydrocarbon groups of 1-4 carbon atoms, aliphatic ether groups, each of said ether groups having a single ether linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (d) aliphatic ether groups each of said groups having a single ether linkage therein and otherwise being hydroxy substituted hydrocarbon of 2-4 carbon atoms, (e) aliphatic ke-to groups, each of said groups having a single keto linkage therein and otherwise being hydrocarbon of 2-4 carbon atoms, (f) aliphatic keto groups, each of 'said groups having a single keto linkage therein and otherwise being hydroxy substituted hydrocarbon of 24 carbon atoms; R3 is a hydrocarbon radical selected from the group consisting of (h) aliphatic hydrocarbon radicals of 618 carbon atoms, and (i) aliphaticaromatic hydrocarbon radicals consisting of benzene and naphthalene groups each having .an aliphatic hydrocarbon radical of 6l8 carbon atoms attached thereto; X is selected from the group consisting of 0503 and S03; and M is an alkali metal.

9. The method comprising to a solution containing a compound of Formula I and a compound of Formula II both defined in claim 8, adding a quantity of an acidic agent to lower the pH thereof to a value of approximately 30 7 to approximately 9 and maintaining the temperature of the mass between about 100 F. and 200 F.

III-The method comprising to a solution whose pH i at least 1.0 and containing a compound of Formula I and a compound of Formula II both defined in claim 8, add ing a quantity of an acidic agent to lower the pH thereof to. a value of approximately 7 to approximately 9 and maintaining the temperature of the mass between about F. and, 200 F. r

11. The method defined in claim 8, with the mole ratio of compound of Formula I to compound of Formula II being 2 moles of the former to 13 moles of the latter.

12. The method defined in claim 9, with the mole ratio of compound of Formula I to compound of Formula II being 2 moles of the former to 1-3 moles of the latter.

13. The method defined in claim 10, with the mole ratio of compound of Formula I to compound of Formula II being 2 moles of the former to 1-3 moles of the latter.

14:.v A novel compound of the following formula:

/Cg: N OH: I

I /C:H4-OH C1lH2a-C-N J CHa-OOONa C1zH25-O 03 References Cited in the file of this patent UNITED STATES PATENTS 2,267,965 Wilson Dec. 30, 1941 2,268,273 Wilkes et al. Dec. 30, 1941 2,528,378 Mannheimer Oct. 31, 1950 

1. A NOVEL COMPOUND OF THE FOLLOWING FORMULA: 